Photopolymerizable composition for color filter and color filter prepared therefrom

ABSTRACT

The present invention relates to a photopolymerizable composition containing a photopolymerizable compound having at least one ethylenically unsaturated double bond, a photopolymerization initiator, a pigment and optionally another resin, wherein said photopolymerizable compound contained therein comprises not less than 60%.

TECHNICAL FIELD

The present invention relates to a composition for color filter and acolor filter prepared therewith. More particularly, the presentinvention relates to a photopolymerizable composition for color filterhaving an excellent optical property for use in a liquid crystal displaydevice, a color separation device, a sensor, and the like, and a colorfilter prepared therewith.

BACKGROUND TECHNOLOGY

A color filter used for a color image pick-up device which finds a bigdemand for a VTR camera and a color copying machine, and for a liquidcrystal color display device replacing for a CRT system because of atendency to be lighter and thinner, is formed by providing minute areascolored with at least two kinds of hue, on a solid image pick-up deviceor a transparent substrate.

So far, such a colored thin film has been prepared by dyeing or printingmethod, and when an espcially high definition image is required, thedyeing method has mainly been used.

However, a color filter by the dyeing method is usually manufactured byforming in advance an image on a substrate with a dyeable base material,such as, a natural photosensitive resin, for instance gelatine, an aminemodified polyvinyl alcohol, an amine modified acrylic resin, or thelike, followed by dyeing with a dye such as an acid dye, etc. and, sinceit is necessary to form multiple colors on the same substrate, aprotection process against dyeing must be done every time the color ischanged, and this invites a problem that the process is very complex andlong. Further, as light resistance, heat resistance and moistureresistance of dyes and resins used are generally low, color filtersprepared therewith also have relatively unreliable light, heat andmoisture resistance.

A color filter by the printing method is manufactured by printing withan ink which is prepared by dispersing a pigment in a thermo- orphotosetting resin, and then curing the resin by heat or light. However,with this color filter, a high definition image is difficult to form andthe image obtained has a problem in its surface smoothness. In order tomake the process simpler, a method to disperse or dissolve coloringmatters in the resin in advance has been proposed.

For example, Japanese Patent Application Laid-open (Kokai) Nos.1-152449; 1-254918; 2-153353 and 2-804 propose methods for forming amulticolor pattern by dispersing pigments in a photosensitive resincontaining a multifunctional acrylate monomer and a highly sensitivehalomethyl-s-triazine photopolymerization initiator. These processes aresimpler than the formation of a color filter by the dyeing method. Asthe resins and pigments used have high heat and light resistance, thefilters manufactured by these processes are generally more reliable thanthe filters made by the dyeing method. However, since radicals generatedfrom the photopolymerization initiator during photopolymerization aretrapped by oxygen, those photosensitive resin materials cannot be curedsufficiently under the condition exposed to air. As the result, afterthe photopolymerizable composition is coated and dried, it is necessaryto form a film (an oxygen blocking film) of PVA, etc. further on thecoated composition to block oxygen. Accordingly, there remains sometroubles in view of simplifying the process.

On the other hand, Japanese Patent Application Laid-open (Kokai) Nos.60-129738 and 60-129739 propose a method in which the oxygen film is notrequired. This method employs a coloring composition using aphotosensitive PVA-stilbazolium cross-linking resin. However, since thebase resin is PVA which has low heat resistance and is water soluble,there remains a problem of its moisture resistance. Further, as theboiling point of water is low, it is disadvantageous to spin-coat thecomposition on a large size substrate.

DISCLOSURE OF THE INVENTION

An object of the present invention is to develop a photopolymerizablecomposition for a color filter which has excellent light and heatresistance, and good image resolution and can be manufactured by asimple process.

The present inventors have extensively studied to find out a method forthe preparation of a color filter which-has excellent light and heatresistance, and good image resolution and can be manufactured by asimple process as described before and as a result have found that aspecific photopolymerizable composition can fulfil the aforementionedfeatures. Accordingly, the present invention has been attained.

Namely, the present invention provides:

(1) A photopolymerizable composition for color filter containing aphotopolymerizable compound having at least one ethylenicallyunsaturated double bond, a photopolymerization initiator, a pigment andoptionally another resin, characterized in that said photopolymerizablecompound contained comprises not less than 60%.

(2) The photopolymerizable composition for color filter described initem (1) above, wherein the photopolymerizable compound is aphotopolymerizable compound having an average molecular weight of notless than 1000.

(3) The photopolymerizable composition for color filter described initem (1) above, wherein the photopolymerization initiator is a mixturecomprising a compound represented by the formula (1): ##STR1## athioxanthone compound and optionally another photopolymerizationinitiator.

(4) The photopolymerizable composition for color filter described initem (3) above, wherein the other photopolymerization initiatorcomprises a hexaaryl-bisimidazole compound and a hydrogen donor.

(5) The photopolymerizable composition for color filter described initem (4) above, wherein the hydrogen donor is an aromatic mercaptan.

(6) The photopolymerizable composition for color filter described initem (4) above, wherein said hydrogen donor is an aromatic amine.

(7) The photopolymerizable composition for color filter described initem (5) above, wherein the aromatic mercaptan is2-mercaptobenzothiazole or 2-mercaptobenzoxazole.

(8) The photopolymerizable composition for color filter described initem (1) above, wherein the photopolymerizable compound is a compoundhaving an ethylenically unsaturated double bond and a carboxyl group.

(9) The photopolymerizable composition for color filter described initem (8) above, wherein the photopolymerizable compound having anethylenically unsaturated double bond and a carboxyl group is a compoundrepresented by the formula (2): ##STR2## wherein X represents ##STR3##but at least one of X is represented by the formula (b); R₁, R₂ and R₃independenly represent a hydrogen atom or a methyl group; A representsan aliphatic or cyclic hydrocarbon chain; and n is a number of from 0 to20.

(10) The photopolymerizable composition for color filter described initem (8) above, wherein the photopolymerizable compound having anethylenically unsaturated double bond and a carboxyl group is a compoundrepresented by the formula (3): ##STR4## wherein X represents ##STR5##but at least one of X is represented by the formula (b); R₁, R₂ and R₃independently represent a hydrogen atom or a methyl group; and Arepresents an aliphatic or cyclic hydrocarbon chain.

(11) The photopolymerizable composition for color filter described initem (8) above, wherein the photopolymerizable compound having anethylenically unsaturated double bond and a carboxyl group is a compoundrepresented by the formula (4): ##STR6## wherein X represents ##STR7##but at least one of X is represented by the formula (b), R represents ahydrogen atom or a methyl group, and A represents an aliphatic or cyclichydrocarbon chain.

(12) The photopolymerizable composition for color filter described initem (8) above, wherein the photopolymerizable compound having anethylenically unsaturated double bond and a carboxyl group is a compoundrepresented by the formula (5): ##STR8## wherein X represents ##STR9##but at least one of X is represented by the formula (b), R₁, R₂ and R₃independently represent a hydrogen atom or a methyl group, and Arepresents an aliphatic or cyclic hydrocarbon chain.

(13) The photopolymerizable composition for color filter described initem (8) above, wherein the photopolymerizable compound having anethylenically unsaturated double bond and a carboxyl group is a compoundrepresented by the formula (6): ##STR10## wherein A represents ##STR11##but at least one of A is represented by the formula (d), R represents ahydrogen atom or a methyl group, n is from 1 to 3 and m is from 1 to 20.

(14) The photopolymerizable composition for color filter described initem (1) above, which contains a compound having an epoxy group asanother resin.

(15) The photopolymerizable composition for color filter described initem (1) above, wherein the pigment is a pigment treated with adispersing agent and a derivative of coloring matter.

(16) A color filter obtained from the photopolymerizable composition forcolor filter described in items (1) to (14).

Further, in the above formulae, although the ratio (a):(b) or (c):(d)can arbitrarily be selected according to development conditions used,the ratios (a):(b) and (c):(d) are usually in a range of 2:1 to 1:3,preferably 1:1 to 1:2.

The photopolymerizable composition for color filter of the inventionwill be described in detail.

In the present invention, the photosensitive resin composition isprepared so that the proportion of the photopolymerizable compound inthe photosensitive resin is not less than 60%, in order to carry outefficiently photpolymerization under exposure to the atmosphere. As thecompound having at least one ethylenically unsaturated double bond, thefollowing compounds may be exemplified;

Esters of monovalent or multivalent alcohols and acrylic acid ormethacrylic acid, such as, ethyl acrylate, butyl acrylate, hydroxyethylacrylate, hydroxyethyl methacrylate, ethylene glycol dimethacrylate,pentaerythritol triacrylate, pentaerythritol trimethacrylate,dipentaerythritol hexaacrylate, and dipentaerythritol hexamethacrylate;conventional photopolymerizable resins, for example, polyester(meth)acrylates which are obtained by reacting (meth) acrylic acid withpolyester prepolymers which can be obtained by condensing multivalentalcohols and monobasic or multibasic acids; polyurethane (meth)acrylateswhich are obtained by reacting a polyol group and a compound having twoisocyanate groups followed by reaction with (meth)acrylic acid; andepoxy(meth)acrylates which are obtained by reacting (meth)acrylic acidwith epoxy resins, such as, bisphenol-A type epoxy resins, bisphenol-Ftype epoxy resins, novolak-type epoxy resins, polycarboxylic acidglycidyl esters, polyol polyglycidyl esters, aliphatic or aticyclicepoxy resins, amine epoxy resins, triphenolmethane type epoxy resins,and dihydroxybenzene type epoxy resins; can be exemplified.

Among these photopolymerizable compounds, those having an averagemolecular weight of not less than 1,000 have a high photopolymerizationrate under exposure to atmosphere and it is particularly useful to usethese compounds in the photosensitive resin compositions. Thephotopolymerizable compounds described above can be used alone or as amixture thereof.

As another resin which may optionally be used in the photopolymerizablecomposition of the present invention, there can be exemplified (filmforming) polymer binders. As examples of such polymer binders, anyorganic polymer binder can be used as far as it is compatible with thephotopolymerizable resin described before. For example, polymethacrylicacid esters or their partial hydrolysates; polyvinyl acetate or itshydrolysate; polystyrene; polyvinylbutyral; polychloroprene; polyvinylchloride; chlorinated polyethylene; chlorinated polypropylene; polyvinylpyrrolidone; copolymers of styrene and maleic anhydride or their halfesters; and copolymers having a glass transition point of not lower than35° C. and selected from copolymerizable monomers, such as, acrylicacid, acrylic esters, methacrylic acid, methacrylic esters, acrylamideand acrylonitrile. Among them, those having an acidic group such as acarboxyl group can be developed in water and are more advantageous inview of economy and safety in comparison with those which are developedonly in an organic solvent.

The above described polymer binders are used within the range of nothigher than 40% by weight in the photosensitive resin according tonecessity.

In the present invention, a photopolymerizable compound having an acidicgroup such as carboxyl group in combination with an ethylenicallyunsaturated double bond may also be used. These compounds are useful inincreasing the proportion of photopolymerizable compounds having anethylenically unsaturated double bond in the photosensitive resin,thereby increasing the polymerization rate under exposure to theatmosphere and permitting development in water, although the abovedescribed polymer binders are compounds which are not involved in thephotopolymerization.

As an illustrative example, the following can be exemplified.

Namely, epoxy (meth)acrylate-carboxylic acid adducts obtained byreacting (meth)acrylic acid with the epoxy group of epoxy resins, suchas, bisphenol-A type epoxy resin, bisphenol-F type epoxy resin, novolaktype epoxy resin, polycarboxylic acid glycidyl ester, polyolpolyglycidyl ester, aliphatic or alicyclic epoxy resin, amine epoxyresin, triphenolmethane type epoxy resin, and dihydroxybenzene typeepoxy resin and reacting an acid anhydride with the hydroxyl groupobtained; half-esterified compounds obtained by reacting an acrylatehaving an alcoholic hydroxyl group such as hydroxyethyl acrylate, or anacrylate having an epoxy group, such as glycidyl methacrylate, with themaleic anhydride moiety of a copolymer of maleic anhydride and acopolymerizable monomer, such as, ethylene, propene, isobutylene,styrene, vinylphenol, acrylic acid, acrylic ester, acrylamide; andcompounds obtained by reacting acrylic acid with the hydroxyl group of acopolymer of acrylic acid or acrylic ester and an acrylate having analcoholic hydroxyl group, such as hydroxyethyl acrylate, can beexemplified. These compounds can be used alone or in a mixture thereof.Further, they can be used together with the photoplymerizable compounddescribed before and are used so that the total weight thereof is notless than 60% of the photosensitive resin.

Further, as the photopolymerizable compound having an ethylenicallyunsaturated double bond and a carboxyl group, compounds respresented bythe above-described formulae (2), (3), (4), (5) and (6) are especiallypreferred.

In the present invention, an epoxy compound can be used as an optionalcomponent to improve the heat resistance. Epoxy compounds thermallyreact with the above described compounds having a carboxylic acid andimproves the heat resistance by cross-linking. As illustrative examplesof epoxy compounds, bisphenol-A type epoxy resin, bisphenol-F type epoxyresin, novolak type epoxy resin, polycarboxylic acid glycidyl ester,polyol polyglycidyl ester, aliphatic or alicyclic epoxy resin, amineepoxy resin, triphenolmethane type epoxy resin, and dihydroxybenzenetype epoxy resin can be exemplified. If necessary, these compounds areused within the range of not more than 30%, more preferably not morethan 20%, based on the weight of photosensitive resin.

As a photopolymerization initiator used in the present invention,various initiators can be used alone or in a mixture. Generally, incolored photopolymerizable resins having pigments dispersed therein,ultraviolet light, which is required for the initiator to generateradicals, may be absorbed by the pigments and radicals are notsufficiently generated; thus, the polymerization may be insufficient.Accordingly, it is necessary to use a highly sensitive compound orcomposition as the photopolymerization initiator. As an illustrativeexample of the photopolymerization initiator which may be used, benzyl;benzoin ether; benzoin isobutyl ether; benzoin isopropyl ether;benzophenone; benzoylbenzoic acid; methyl benzoylbenzoate;4-benzoyl-4'-methyldiphenyl sulfide; benzylmethylketal;2-n-butoxyethyl-4-dimethylaminobenzoate; 2-chlorothioxanthone;2,4-diethylthioxanthone; 2,4-diisopropylthioxanthone;dimethylaminomethylbenzoate; isoamyl p-dimethylaminobenzoate;3,3'-dimethyl-4-methoxybenzophenone; 2,4-dimethylthioxanthone;1-(4-dodecylphenyl)-2-hydroxy-2-methylpropan-1-on;1-hydroxycyclohexylphenyl ketone;2-hydroxy-2-methyl-1-phenylpropan-1-on;1-(4-isopropylphenyl)-2-hydroxy-2-methylpropan-1-on;isopropylthioxanthone; methylbenzoyl formate; and2-methyl-1-[4-(methylthio)phenyl]-2-morpholinopropan-1-on can beexemplified. These photopolymerization initiators can be used alone orin a mixture thereof. The amount thereof usd in the photosensitive resinis 0.1 to 20%, preferably 1 to 10%.

When the photopolymerization initiator is used in the form of acomposition in the present invention, a preferable composition havingparticulaly high polymerization rate is a combination of a compoundrepresented by the formula (1) described before and a thioxanthonecompound. As an illustrative example of such thioxanthone compound,2-chlorothioxanthone, 2,4-dimethylthioxanthone, 2,4-diethylthioxanthone,2,4-diisopropylthioxanthone and isopropylthioxanthone as mentioned abovecan be exemplified.

The compound represented by the above mentioned formula (1) and thethioxanthone compound are each used in an amount of 0.1 to 10% byweight, preferably 0.1 to 5% by weight, of the photosensitive resin.

Further, as a photopolymerization iniator in the present invention, ahexaarylbisimidazole compound and a hydrogen donor can be used inaddition to the mixture of a compound represented by the formula (1)described above and the thioxanthone compound.

Examples of hexaarylbisimidazole compound are disclosed in U.S. Pat. No.3,784,557 or EP-A-24629. Those which are especially good in stabilityand sensitivity include2,2'-bis(o-chlorophenyl)-4,4',5,5'-tetra-(p-methoxyphenyl)-bisimidazolyland the compound is used in 0.1 to 10% by weight, preferably 0.1 to 5%by weight, based on the photosensitive resin.

As the hydrogen donor, an aromatic mercaptan compound and an aromaticamine compound can be usd. As the aromatic mercaptan hydrogen donor, acompound which has a benzene or heterocyclic ring as a base structureand one or two mercapto groups is good. When the donor has twosubstituent groups, one mercapto group may be substituted by an alkyl,aralkyl or phenyl group or the donor may be a dimer in the form of adisulfide.

As a preferable example, 2-mercaptobenzothiazole and2-mercaptobenzoxazol, etc. can be exemplified. The amount of the donorused is 0.1 to 10% by weight, preferably 0.1 to 5% by weight, based onthe photosensitive resin.

As the aromatic amine hydrogen donor, a compound which has a benzene orheterocyclic ring as a base structure and one or two amino groups isgood. The amino group may be substituted with an alkyl group or asubstituted alkyl group. The monoamino substituted compound may befurther substituted with a carboxy group, an alkoxycarbonyl group, asubstituted alkoxycarbonyl group, a phenoxycarbonyl group, a substitutedphenoxycarbonyl group or a nitryl group. As a particularly preferableone, compounds represented by the following formulae (7) to (12) can beexemplified. ##STR12##

These may optionally be used in an amount of 0.1 to 10% by weight,preferably 0.1 to 5% by weight, based on the photosensitive resin.

Since transparency to visible light is required, pigments used in thephotopolymerizable composition for color filter of the present inventiondesirably have a particle size which is not larger than half of wavelength of transmitting visible light, and preferably pigments dispersedin a number average particle size of not larger than 200 nm is moredesirable. It is usually preferable that these pigments are dispersed bymeans of a dispersing agent and an organic solvent. As the organicsolvent, ethylcellosolve, methylcellosolve, propylcellosolve,butylcellosolve or an acetylated product of these cellosolves is used.

As preferable examples, phthalocyanine pigments, etc. for blue pigments;quinacridone pigments, perylene pigments, pyrrolo pyrrole pigments,anthraquinone pigments, etc. for red pigment; and halogenatedphthalocyanine pigments for green pigment can be exemplified. Thesepigments can be usd alone or in a combined (toning) form. Further, as apigment for black matrix, carbon, titan carbon, iron oxide, azo blackpigment, etc. can be used alone or in combination.

These fine particle pigment is used in the range of 10 to 60% by weight,preferably 20 to 50% by weight, based on the photosensitive resin.

The photopolymerizable composition of the present invention is usuallydiluted with an organic solvent when used. As the organic solvent,although any solvent which can dissolve all components of thephotopolymerizable composition of the present invention except pigmentmay be used, those solvents which do not have a tendency to dry duringcoating process with a coating machine such as spinner, etc. and whichevaporate slowly, are preferably used as good solvent. An illustrativeexample of such organic solvents may include ethylcellosolve,methylcellosolve, propylcellosolve, butylcellosolve or an acetylatedproduct of these cellosolves. The photopolymerizable composition of thepresent invention is usually dissolved with an organic solvent of 1 to 5times (weight ratio) the weight of solid substances in the composition.

The photopolymerizable composition for color filter of the presentinvention can be obtained by mixing the photopolymerizable compound(s),the photopolymerization initiator(s), the pigment(s), the solvent(s) andoptionally other resin(s) in ratios described above. The mixing ispreferably performed by treating with a usual mixer or a disperser. Theobtained photopolymerizable composition for color filter of the presentinvention may be filtered to remove coarse particles and foreignmatters. In the filtration, a filter having a pore size of not largerthan 1 μm, preferably not larger than 0.5 μm, is used.

A general process for manufacturing a color filter with thephotopolymerizable composition of the present invention is as follows.

The photopolymerizable composition of the present invention is dissolvedin the solvent, and the solution is coated on a substrate for electronicpart, such as glass plate, plastic plate, silicon wafer for imagepick-up device, etc. in a thickness in dry state of 0.5 to 10 μm,preferably 1 to 3 μm, followed by drying the solvent to form smoothcoated film. Ultra violet rays are irradiated through a negative mask onthe coated film to form a desired image. In the irradiation, it ispreferable to use a device, such as mask alignment, etc. to irradiatethe film surface uniformly with parallel rays. Then, after promoting thepolymerization of the irradiated film by heating for a short time, thefilm is exposed to a flow or shower of a development liquid anddeveloped it by dissolving an unsolidified part. With this development,the desired image (color filter) is obtained.

BRIEF EXPLANATION OF THE DRAWING

FIG. 1 is a spectrum of a color filter obtained in ApplicationExample 1. In the figure, the abscissa represents wave length (nm) andthe ordinate represents absorbance.

THE BEST MODE OF PRACTICING THE PRESENT INVENTION

Hereinafter, the present invention will be described more in detail, butthe present invention is not limited to these examples only.

EXAMPLE 1

A photosensitive resin composition having the following composition wasprepared.

(Photopolymerizable Compound)

13.5 g of KAYARAD DPHA, manufactured by Nippon Kayaku (acrylic estercompound);

18.0 g of KAYARAD R2089, manufactured by Nippon Kayaku (acrylic estercompound).

(Polymer Binder)

13.5 g of SMA2625, manufactured by Arco Chemical (copolymer of styreneand maleic acid).

(Photopolymerization Initiator)

1.0 g of 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)butanone; and

0.5 g of 2,4-diethylthioxanthone.

(Solvent)

100.0 g of ethyl cellosolve acetate.

Pastes of fine particle pigments of red, green, blue and black to beadded to the photosensitive resin composition described above wereprepared as follows. In Table 1, the mixing ratio is by weight.

                  TABLE 1                                                         ______________________________________                                        Pigments Used and Their Mixing Ratio                                                 Pigment used    Mixing Ratio                                           ______________________________________                                        Red      CI Pigment red 177    75                                                      CI Pigment yellow                                                                            83     25                                             Green    CI Pigment green                                                                             36     90                                                      CI Pigment yellow                                                                            83     10                                             Blue     CI Pigment blue                                                                              15     95                                                      CI Pigment violet                                                                            23      5                                             Black    Carbon black          100                                            ______________________________________                                    

To 20 g of each mixture of the pigments described above, 4 g of sorbitanfatty acid ester compound was added as dispersing agent, and 76 g ofethyl cellosolve acetate was further added. The mixture was dispersedwith a sand mill.

Further, a dispersion having excellent fluidity was obtained whenconventionally known pigment derivatives were added and dispersed in thesame manner as described above.

Each average particle number distribution of the dispersed particles ofred, green, and blue pigments was not more than 200 nm. 40% by weight ofthe paste of fine particle pigments was added to the above describedphotosensitive resin composition, treated with a sand mill, and filteredthrough a 1 μm filter of a filter press to obtain a photopolymerizablecomposition for color filter.

Application Example 1

On a smooth glass plate washed with water, alcohol, then fleon, thephotopolymerizable composition for color filter obtained in Example 1was coated by a spin coater, and dried at 100° C. for 5 minutes. Thusobtained coated film was exposed to light through a negative mask byMaskaligner-MA-10 (manufactured by Mikasa Co., Ltd.) under atmosphericenvironment. Then, the film was prebaked at 100° C. for 15 minutes, anddeveloped by a flow of 1% by weight of aqueous sodium carbonate solutionat 25° C. for 60 seconds to obtain a color filter.

The coated film thickness of the color filter for each color obtained inthe above described manner is shown below.

                  TABLE 2                                                         ______________________________________                                        Pigment      Film Thickness                                                   ______________________________________                                        Red          2.0μ                                                          Green        2.0μ                                                          Blue         1.6μ                                                          Black        0.8μ                                                          ______________________________________                                    

The spectra of the color filters obtained under the above conditions areshown in FIG. 1.

Examples 2 to 42 and Application Examples 2 to 42

Photopolymerizable compositions for color filter were prepared in thesame manner as in Example 1 using resin compositions shown in Tables 3to 16 and color filters were prepared in the same manner as inApplication Example 1. Raw materials used are shown below.

Group A (Photopolymerizable Compound)

(1) KAYARAD DPHA, manufactured by Nippon Kayaku (acrylic estercompound).

(2) KAYARAD RP1040, manufactured by Nippon Kayaku (acrylic estercompound).

(3) KAYARAD TMPTA, manufactured by Nippon Kayaku (acrylic estercompound).

(4) KAYARAD FM100, manufactured by Nippon Kayaku (acrylic estercompound).

(5) Dipentaerythritolhexamethacrylate.

(6) KAYARAD R2089, manufactured by Nippon Kayaku (acrylic estercompound). ##STR13##

Group B (Polymer binder)

(9) SMA2625, manufactured by Arco Chemical (copolymer of styrene andmaleic acid).

(10) SMA17352, manufactured by Arco Chemical (copolymer of styrene andmaleic acid).

(11) Copolymer of benzyl methacrylate and methacrylic acid (molar ratio:70/30).

(12) Copolymer of ethyl methacrylate and methacrylic acid (molar ratio:70/30).

Group C (Compound having ethylenically unsaturated double bond andcarboxyl group).

(13) KAYARAD R849, manufactured by Nippon Kayaku.

(14) KAYARAD R5107, manufactured by Nippon Kayaku.

(15 ) KAYARAD R5197, manufactured by Nippon Kayaku.

(16) KAYARAD R5201, manufactured by Nippon Kayaku. ##STR14## wherein xrepresents ##STR15## and the ratio of (a') to (b') is 1:2. ##STR16##wherein X represents ##STR17## and the ratio of (a') to (b') is 1:2.##STR18##

Group D (Epoxy resin)

(20) AK601 manufactured by Nippon Kayaku (glycidyl ester compound).

(21) XGE manufactured by Nippon Kayaku (epoxy compound).

(22) RGE manufactured by Nippon Kayaku (epoxy compound).

(23) Epicoat 828 manufactured by Yuka Shell Epoxy (epoxy compound).

Group E (Photopolymerization initiator)

(24) IRGACURE 369 manufactured by Ciba-Geigy.

(25) IRGACURE 907 manufactured by Ciba-Geigy.

(26) KAYACURE DETX manufactured by Nippon Kayaku.

(27) KAYACURE EPA manufactured by Nippon Kayaku.

(28) I sop ropy lthioxanthone.

(29) 2,2'-bis(o-chlorophenyl)-4,4',5,5'-tetraphenylbisimidazolyl.

(30)2,2'-bis(o-chlorophenyl)-4,4',5,5'-tetra(p-methoxyphenyl)bisimidazolyl.

(31) 2-mercaptobenzothiazole.

(32) 2-mercaptobenzoxazole.

(33) Miharase ketone.

(34) 4-(p-methoxyphenyl)-2,6-di(trichloromethyl)-s-triazine.

                  TABLE 3                                                         ______________________________________                                               Example 2 Example 3   Example 4                                        ______________________________________                                        Group A   (1)   9.0 g     (2) 13.0 g  (3) 9.0 g                                         (6)   23.3 g    (6) 18.0 g  (6) 23.3 g                              Group B   (9)   11.3 g    (9) 13.5 g  (9) 11.3 g                              Group C         --            --          --                                  Group D         --            --          --                                  Group E  (24)   2.0 g    (24)  1.0 g (24) 2.0 g                                        (26)   1.0 g    (26)  0.5 g (26) 1.0 g                                        (29)   0.5 g         --     (30) 1.0 g                                        (31)   0.5 g         --     (32) 1.0 g                               ______________________________________                                    

                  TABLE 4                                                         ______________________________________                                               Example 5 Example 6   Example 7                                        ______________________________________                                        Group A   (4)   13.0 g    (1) 9.0 g   (4) 13.0 g                                        (6)   18.0 g    (7) 23.3 g  (8) 18.0 g                              Group B   (9)   13.5 g    (9) 11.3 g  (9) 13.5 g                              Group C         --            --          --                                  Group D         --            --          --                                  Group E  (24)    1.0 g   (24) 2.0 g  (24) 1.0 g                                        (28)    0.5 g   (28) 1.0 g  (26) 0.5 g                                               --       (29) 0.5 g  (30) 0.5 g                                               --       (31) 0.5 g  (32) 0.5 g                               ______________________________________                                    

                  TABLE 5                                                         ______________________________________                                               Example 8 Example 9   Example 10                                       ______________________________________                                        Group A   (1)    9.0 g    (1) 13.0 g  (1) 9.0 g                                         (6)   23.3 g    (6) 18.0 g  (6) 23.3 g                              Group B  (10)   11.3 g   (11) 13.5 g (12) 11.3 g                              Group C         --            --          --                                  Group D         --            --          --                                  Group E  (34)    2.0 g   (25)  1.0 g (25) 2.0 g                                               --       (26)  0.5 g (28) 1.0 g                                               --            --     (29) 1.0 g                                               --            --     (31) 1.0 g                               ______________________________________                                    

                  TABLE 6                                                         ______________________________________                                               Example 11                                                                              Example 12  Example 13                                       ______________________________________                                        Group A   (6)   20.3 g    (6) 15.8 g  (6) 18.0 g                                        (1)   11.2 g    (1) 11.2 g  (1) 9.0 g                               Group B         --            --          --                                  Group C         --            --          --                                  Group D  (13)   13.5 g   (13) 18.0 g (13) 18.0 g                              Group E  (24)   2.0 g    (24) 2.0 g  (24) 2.0 g                                        (26)   1.0 g    (26) 1.0 g  (26) 1.0 g                                        (29)   1.0 g    (29) 1.0 g  (29) 0.5 g                                        (33)   1.0 g    (27) 1.0 g  (31) 0.5 g                               ______________________________________                                    

                  TABLE 7                                                         ______________________________________                                               Example 14                                                                              Example 15  Example 16                                       ______________________________________                                        Group A   (6)   15.8 g    (6) 13.5 g  (6) 15.8 g                                        (1)   8.1 g     (1) 9.0 g   (1) 8.1 g                               Group B         --            --          --                                  Group C         --            --          --                                  Group D  (14)   21.1 g   (15) 22.5 g (16) 21.1 g                              Group E  (24)   2.0 g    (24) 1.0 g  (24) 2.0 g                                        (26)   1.0 g    (26) 0.5 g  (26) 1.0 g                                        (29)   0.5 g         --     (30) 1.0 g                                        (31)   0.5 g         --     (32) 1.0 g                               ______________________________________                                    

                  TABLE 8                                                         ______________________________________                                               Example 17                                                                              Example 18  Example 19                                       ______________________________________                                        Group A   (6)   13.5 g    (6) 13.5 g  (6) 18.0 g                                        (1)   9.0 g     (1) 9.0 g   (1) 13.5 g                              Group B         --            --          --                                  Group C         --            --          --                                  Group D  (17)   22.5 g   (18) 22.5 g (19) 13.5 g                              Group E  (24)   1.0 g    (24) 2.0 g  (24) 1.0 g                                        (28)   0.5 g    (28) 1.0 g  (26) 0.5 g                                               --       (29) 0.5 g  (30) 0.5 g                                               --       (31) 0.5 g  (32) 0.5 g                               ______________________________________                                    

                  TABLE 9                                                         ______________________________________                                               Example 20                                                                              Example 21  Example 22                                       ______________________________________                                        Group A   (7)   20.3 g    (8) 15.8 g  (6) 18.0 g                                        (1)   11.2 g    (1) 11.2 g  (2) 9.0 g                               Group B         --            --          --                                  Group C         --            --          --                                  Group D  (13)   13.5 g   (13) 18.0 g (13) 18.0 g                              Group E  (34)   2.0 g    (25) 1.0 g  (25) 2.0 g                                               --       (26) 0.5 g  (28) 1.0 g                                               --            --     (29) 1.0 g                                               --            --     (31) 1.0 g                               ______________________________________                                    

                  TABLE 10                                                        ______________________________________                                               Example 23                                                                              Example 24  Example 25                                       ______________________________________                                        Group A   (6)   15.8 g    (6) 13.5 g  (6) 15.8 g                                        (3)   8.1 g     (4) 9.0 g   (5) 8.1 g                               Group B         --            --          --                                  Group C         --            --          --                                  Group D  (14)   21.1 g   (15) 22.5 g (16) 21.1 g                              Group E  (24)   2.0 g    (24) 2.0 g  (24) 2.0 g                                        (26)   1.0 g    (26) 1.0 g  (26) 1.0 g                                        (29)   1.0 g    (29) 1.0 g  (29) 0.5 g                                        (33)   1.0 g    (27) 1.0 g  (31) 0.5 g                               ______________________________________                                    

                  TABLE 11                                                        ______________________________________                                               Example 26                                                                              Example 27  Example 28                                       ______________________________________                                        Group A   (6)   19.3 g    (6) 18.3 g  (6) 19.3 g                                        (1)   10.6 g    (1) 10.0 g  (1) 10.6 g                              Group B         --            --          --                                  Group C  (20)   2.3 g    (20) 4.5 g  (21) 2.3 g                               Group D  (13)   12.8 g   (13) 12.2 g (13) 18.0 g                              Group E  (24)   2.0 g    (24) 1.0 g  (24) 2.0 g                                        (26)   1.0 g    (26) 0.5 g  (26) 1.0 g                                        (29)   0.5 g         --     (30) 1.0 g                                        (31)   0.5 g         --     (32) 1.0 g                               ______________________________________                                    

                  TABLE 12                                                        ______________________________________                                               Example 29                                                                              Example 30  Example 31                                       ______________________________________                                        Group A   (6)   18.3 g    (6) 19.3 g  (6) 18.3 g                                        (1)   10.0 g    (1) 10.6 g  (1) 10.0 g                              Group B         --            --          --                                  Group C  (21)   4.5 g    (22) 2.3 g  (22) 4.5 g                               Group D  (13)   12.2 g   (13) 12.8 g (13) 12.2 g                              Group E  (24)   1.0 g    (24) 2.0 g  (24) 2.0 g                                        (26)   0.5 g    (26) 1.0 g  (26) 1.0 g                                        (29)   0.5 g    (29) 0.5 g  (29) 0.5 g                                        (31)   0.5 g    (31) 0.5 g  (31) 0.5 g                               ______________________________________                                    

                  TABLE 13                                                        ______________________________________                                               Example 32                                                                              Example 33  Example 34                                       ______________________________________                                        Group A   (6)   19.3 g    (6) 18.3 g  (6) 15.3 g                                        (1)   10.6 g    (1) 10.0 g  (1) 14.6 g                              Group B         --            --          --                                  Group C  (23)   2.3 g    (23) 4.5 g  (22) 4.5 g                               Group D  (13)   12.8 g   (13) 12.2 g (13) 12.8 g                              Group E  (24)   2.0 g    (24) 2.0 g  (24) 2.0 g                                        (26)   1.0 g    (26) 1.0 g  (26) 1.0 g                                        (29)   0.5 g    (29) 0.5 g  (29) 0.5 g                                        (31)   0.5 g    (31) 0.5 g  (31) 0.5 g                               ______________________________________                                    

                  TABLE 14                                                        ______________________________________                                               Example 35                                                                              Example 36  Example 37                                       ______________________________________                                        Group A   (6)   15.0 g    (6) 12.8 g  (6) 15.0 g                                        (1)   7.7 g     (1) 8.6 g   (1) 7.7 g                               Group B         --            --          --                                  Group C  (20)   2.3 g    (20) 2.3 g  (20) 2.3 g                               Group D  (14)   20.0 g   (15) 21.4 g (16) 20.0 g                              Group E  (24)   2.0 g    (24) 1.0 g  (24) 2.0 g                                        (26)   1.0 g    (26) 0.5 g  (26) 1.0 g                                        (29)   0.5 g         --     (30) 1.0 g                                        (31)   0.5 g         --     (32) 1.0 g                               ______________________________________                                    

                  TABLE 15                                                        ______________________________________                                               Example 38                                                                              Example 39  Example 40                                       ______________________________________                                        Group A   (6)   12.8 g    (6) 12.8 g  (6) 17.1 g                                        (1)   8.6 g     (1) 8.6 g   (1) 12.8 g                              Group B         --            --          --                                  Group C  (20)   2.3 g    (20) 2.3 g  (20) 2.3 g                               Group D  (17)   21.4 g   (18) 21.4 g (19) 12.8 g                              Group E  (24)   1.0 g    (24) 2.0 g  (24) 1.0 g                                        (28)   0.5 g    (28) 1.0 g  (26) 0.5 g                                               --       (29) 0.5 g  (30) 0.5 g                                               --       (31) 0.5 g  (32) 0.5 g                               ______________________________________                                    

                  TABLE 16                                                        ______________________________________                                                 Example 41       Example 42                                          ______________________________________                                        Group A     (6)   19.3 g       (6) 18.3 g                                                 (1)   10.6 g       (1) 10.0 g                                     Group B     (9)   6.4 g        (9) 6.1 g                                      Group C           --          (20) 4.5 g                                      Group D    (13)   6.4 g       (13) 6.1 g                                      Group E    (24)   2.0 g       (24) 1.0 g                                                 (26)   1.0 g       (26) 0.5 g                                                 (29)   0.5 g       (29) 0.5 g                                                 (31)   0.5 g       (31) 0.5 g                                      ______________________________________                                    

Comparative Example 1

A photopolymerizable composition for color filter was prepared using thefollowing resin mixture in the same manner as in Example 1.

(Photopolymerizable compound)

18.0 g of KAYARAD DPHA manufactured by Nippon Kayaku.

(Polymer initiator)

1.0 g of 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)butanone, and

0.5 g of 2,4-diethylthioxanthone.

(Solvent)

100.0 g of ethylcellosolve acetate.

A color filter was prepared by using the above composition in the samemanner as in Application Example 1. However, the photopolymerization wasinsufficient and the image exfoliated during its development.

Industrial Utility

A color filter having high image resolution, good heat resistance andlight resistance can be manufactured with a simple process.

What is claimed is:
 1. A photopolymerizable composition for color filtercontaining a photosensitive resin which comprises a photopolymerizablecompound having at least one ethylenically unsaturated double bond, aphotopolymerization initiator, and a pigment characterized in that saidphotopolymerizable compound is contained in an amount not less than 60%by weight of the photosensitive resin and said pigment is used in anamount of 10 to 60% by weight based on the photosensitive resin.
 2. Thephotopolymerizable composition for color filter according to claim 1,wherein said photopolymerization initiator is a mixture comprising acompound represented by the formula (1): ##STR19## a thioxanthonecompound and optionally another photopolymerization initiator.
 3. Thephotopolymerizable composition for color filter according to claim 2,wherein said another photopolymerization initiator comprises ahexaarylbisimidazole compound and a hydrogen donor.
 4. Thephotopolymerizable composition for color filter according to claim 3,wherein said hydrogen donor is an aromatic mercaptan.
 5. Thephotopolymerizable composition for color filter according to claim 4,wherein said aromatic mercaptan is 2-mercaptobenzothiazole or2-mercaptobenzoxazole.
 6. The photopolymerizable composition for colorfilter according to claim 3, wherein said hydrogen donor is an aromaticamine.
 7. The photopolymerizable composition for color filter accordingto claim 1, wherein said photopolymerizable compound is a compoundhaving an ethylenically unsaturated double bond and a carboxyl group. 8.The photopolymerizable composition for color filter according to claim7, wherein said photopolymerizable compound having an ethylenicallyunsaturated double bond and a carboxyl group is a compound representedby the formula (2): ##STR20## wherein X represents ##STR21## but atleast one of X is represented by the formula (b); R₁, R₂ and R₃independently represent a hydrogen atom or a methyl group; A representsan aliphatic or cyclic hydrocarbon chain; and n is a number of from 0 to20.
 9. The photopolymerizable composition for color filter according toclaim 7, wherein said photopolymerizable compound having anethylenically unsaturated double bond and a carboxyl group is a compoundrepresented by the formula (3): ##STR22## wherein X represents ##STR23##but at least one of X is represented by the formula (b); R₁, R₂ and R₃independently represent a hydrogen atom or a methyl group; and Arepresents an aliphatic or cyclic hydrocarbon chain.
 10. Thephotopolymerizable composition for color filter according to claim 7,wherein said photopolymerizable compound having an ethylenicallyunsaturated double bond and a carboxyl group is a compound representedby the formula (4): ##STR24## wherein X represents ##STR25## but atleast one of X is represented by the formula (b), R represents ahydrogen atom or a methyl group, and A represents an aliphatic or cyclichydrocarbon chain.
 11. The photopolymerizable composition for colorfilter according to claim 7, wherein said photopolymerizable compoundhaving an ethylenically unsaturated double bond and a carboxyl group isa compound represented by the formula (5): ##STR26## wherein Xrepresents ##STR27## but at least one of X is represented by the formula(b), R₁, R₂ and R₃ independently represent a hydrogen atom or a methylgroup, and A represents an aliphatic or cyclic hydrocarbon chain. 12.The photopolymerizable composition for color filter according to claim7, wherein said photopolymerizable compound having an ethylenicallyunsaturated double bond and a carboxyl group is a compound representedby the formula (6): ##STR28## wherein A represents ##STR29## but atleast one of A is represented by the formula (d), R represents ahydrogen atom or a methyl group, n is from 1 to 3 and m is from 1 to 20.13. The photopolymerizable composition for color filter according toclaim 1, which further comprises a compound having an epoxy group. 14.The photopolymerizable composition for color filter according to claim1, wherein said pigment is a pigment treated with a dispersing agent anda derivative of coloring matter.
 15. The photopolymerizable compositionfor color filter according to claim 1, wherein said photosensitive resinfurther comprises a binder resin.